High molal amine quaternary ammonium derivatives of alpha-halogen carboxy acid esters of oxyalkylated phenol-aldehyde resins



Patented Jan. 8, 1952 UNITED s TEs PATENT oFncE HIGH MOLAL QUATERNARYAMMO- 1 NIUM DERIVATIVES or ALPHA-HALOGEN I CARBOXY ACID ESTERS FOXYALKYL- ATED PHIENOL'I-ALDEHYDE RESINS Melvin De Groote, UniversityCity, and Bernhard Keiser, Webster Groves, Mm, assignors to PetroliteCorporation, Ltd. poration of Delaware I,

, Wilmington, Del., a cor- No Drawing; Application December 13, 1948,

acid"h'a ving'"not'over Gearbo'n atoms and hydrophile hydroxylatedsynthetic products;'said hydrophile synthetic products being 'oxyalkylation products of r o (A) An alpha-betaalkylerie oxide having not morethan 4 carbon atoms and selected from the class consisting of ethyleneoxide, propylene oxidefbutjylene oxide, glycide, and methylglycide; and.i. V 'An""oxyalkylation-susceptible, "fusible, organic"s'olvent-so1uble, water-insoluble, phenolaldehyde' resin; s'ai'd resinbeing derivedby reaction between 'a difunctional monohydric' phe-' noland air-aldehyde having not over 8 carbon' atoms and reactive towardsaid phenol; said resin being formed in the substantial absence oftrifunctional phenols; sa'd phenol being of' the z m 1 in which R is ahydrocarbon radical having at least 4 and not more than 12 carbon atomsand substituted in the 2,4,6 position; said oxyalkylated resin beingcharacterized by the introduction into the resin molecule of a pluralityof divalent radi cals having the formula (R)n, injwhich R1 is a memberselected from the class consisting o'f-"etliylene radicals, propyleneradicals; butylene" ybutylene radicals, and dis a numeral varying from 1to with the proviso that, at least 2 moles fof alkylene oxide beintroduced for each P en i c eus r Although the herein describedproducts have a number of industrial applications, they are ofparticular value for resolving petroleum emulsions of thewater-in-oiltype that are commonly radicals, hydroxypropylene radicals, and hydrox-'Serial'No. 65,091

. 8 Claims. (01. 260-53) referred to as cut oil, "roily oil, "emulsifiedoil, etc., and which comprise fine droplets of naturally-occurringwaters or brines dispersed in a. more or less permanent state throughoutthe oil which constitutes the continuous phase of the emulsion. Thisspecific application is described and claimed in our co-pendingapplication Serial No. 65,090, filed December 13, 1948, now Patent2,542,005, granted February 20, 1951. The new products are useful aswetting, detergent, and

' leveling agents in the laundry, textile and dyeing industries; aswetting agents and spreaders in the application of asphalt in roadbuilding and the like; as flotation reagents in the flotation separationof various aqueous suspensions containing negatively charged particles,such as sewage, coal washing waste water, and various trade Wastes andthe like; as germicides, insecticides; emulsifying agents, as, forexample, for cosmetics, spray oils, water-repellent textile finishes; aslubricants, etc;

The esters of alpha-halogen monocarboxy acids with oxyalkylatedphenol-aldehyde resins which are converted to the quaternary ammoniumcompounds of the invention are described in our Patent 2,542,005,granted February 20, 1951. The phenol-aldehyde resins and theiroxyalkylation arejdescribed in our Patent 2,499,370, granted March 7,1950. Reference is made to these patents fora description of thephenol-aldehyde resins used, their oxyalkylation and their conversion toalpha-halogen monocarboxy acid esters. For examples of phenol-aldehyderesins, reference is made to Examples 1a through 103:; of Patent2,499,370. For examples of the oxyalkylated resins, reference is made totables in columns 31 through 46 of Patent 2,542,005. For examples of thealpha-halogen monocarboxy acid esters of these oxyalkylated resins,reference is made to Examples 10 through 390 of Patent 2,542,005. Havingobtained a suitable chloroacetate or the like, such .ester can then bereacted with amines of the formula (CH3)2NR in which R is an aliphaticradical having 10 to 22 carbon atoms.

:Such amines .include dimethyldodecylamine, dimethylhexadecylamine,dimethyloctadecenylamine, etc. Such amines are available from varioussources, and some of the most desirable ones are available from sourcessuch as the Onyx Oil 8; Chemical Company, Jersey City, New Jersey.Others can be prepared by purchasing the primary higher fatty acidamines from the Armour Chemical Division, Armour 8; Company, Chicago,Illinois, and replacing the hydrogen atoms by It is to be noted that, inaddition to the amines previously described, certain other amines areofsuch close structure thatthey would serve just as satisfactorily. Oneexample is an amine obtained by treating monoor dialkylated phenol,particularly butylphenol, amylphenol, octylphenol, dibutylphenol,dioctylphenol, or the like, with one or more moles of ethylene oxide,and then converting the terminal hydroxyl group into a chlorine groupand reactingthe chloride with ammonia so as to give the primary amine,which is subsequently methylated so asto yield a tertiary amine havingtwo methyl groups. An amine of this type which is commercially availableis octylphenoxyethoxyethyldimethylamine. The quaternary ammoniumcompounds obtained from this particular type of tertiary dimethyl'atedamine act the same as quaternary compounds derived from the equivalenthigher fatty acid type of amine, such as cetyldimethylamine,octadecyldimethylamine, hexadecyldimethylamine, dodecyldimethylamine,decyldimethylami'ne, octadecenyldimethylamine, etc.

Example 141 400' grams of the xylene-containing alphachloro acid esteridentified as 80 of Patent 2,542,005 were mixed with an equimolaramount, to wit, 6'7 grams of cetyldimethylamine. To the ester-tertiaryamine mixture there was added an amount of xylene equal in weight toabout 25% of: the tertiary amine. In the instant case this was 15.grams. A little xylene was lost during the subsequent reflux period. Theexperiments were conducted so, that in the majority of cases the finalproduct contained approximately 40% xylene. If desired, this xylenecould be elimmated by evaporation or vacuum distillation. In the use ofthe products for demulsification, it is convenient to have the xylenepresent so as to give a non-viscous liquid which can be. handled easily.

The two reactants were refluxed at the boiling point ,of xylene (140 C.)for 2 00 4 hours. 'Tests, in this kind of reactionhave invariablyindicated that the reaction is complete in lessthan2'hours and sometimesin as little. as 30 minutes. How ever, by way of precaution inthi'sexperiment and in subsequent experiments,.such time range of. 2 to, 4hours was employed The final product, withouteliminating the xylene,was. a, deep am.- ber-colored, noneviscous liquid, which. formed a.cloudy solution in. water, and. contained 44.5%. xylene.

Emamplezd The procedure employed wasthe sameas that in Example 1d,except that 400 gramsof theester. identified as 3c of Patent. 2,542,005were reacted; with 57 grams of cetyldimethylaminer The final productcontained 42.5% xylene. The xylene-. containing solution was anon-viscous,- deep amber-colored liquid, that. was readily.v water!soluble.

Example 3d The procedure employed was the same as that in Example 101,except that 400 grams of theester product contained 40.5% xylene. Thexylenecontaining solution was a very viscous, deep 4 amber-coloredliquid, that was not readily watersoluble.

Example 4d- The procedure employed was the same as that in Example 1d,except that 400 grams of the ester identified as 50 of Patent 2,542,005were reacted with 52 grams of cetyldimethylamine. The final productcontained 40.8% xylene. The xylenecontaining solution was a non-viscous,deep amber-colored liquid, which was water-soluble wit s eh b d Example5d The procedure employed was the same as that in Example 1d, exceptthat 400 grams of the ester identified as 230 of Patent 2,542,005 werereacted with 77 grams of cetyldimethylamine. The final product contained39.8% xylene. .The xylene-containing solution was a non-viscous, deepamber-colored, water-soluble liquid.

Example 611 The procedure employed was the same; as that in Example 141,except that 400 grams of the. esteridntified as 24c of Patent 2,542,005were reacted with 65, gramsof cetyldimethylamine. The final productcontained 40.5% xylene. The xylene. containing solution was a,non-viscous, deep. amber-colored, water-soluble liquid.

Example 7d The. procedure employed was, the same as that. in Example1d,. except that. 400' grams. of the; esterv identified as 25c ofPatentv 2,542,005- were reacted with 50 grams of cetyld'imethylami'nc.The, final product contained 39.4% xylene; The xylene containingsolution was. a somewhat, vie.- cous, deep amber-colored liquid,water-soluble but forming a cloudy solution.

Example 8d;

proc u mployed. was: the; same: as that; in Example ld, except that 500grams of the; ester identified, as. we, of Patent. 2,542,005v werereacted; with, 541 grams of cetyldimethylamlne. he final. produ t. co ted 36L6'%, xylene... The XyIene-contaihing solution. was at \ZBW-viscous, eepamben-Qo r d; almost. sol d mass The. procedure.employedlwasthe. Same: in Example 1d, except" that 500' grams ofidentified as 15c of Patent 2,542,005 were reacted with 64 grams ofoctadecenyldimethylamine. The product contained 38.9% xylene and was avery viscous, dark-amber liquid, giving a somewhat cloudy solution.

Eramizlei 10.01:

The procedure employed was; the: same: aathat' in ltxample ld; except"that- 500 grams of'the; ester. dentified.- as; 1 Qf -ate t" 1542-0105;werereaictedi wlth ejs". grams of dodecyldimethylamihej. ro ctontain45.3%v y ne and was. a. visa co s dark am qu d game. a somewhat. cloudysolution.-

Emamplelld.

- The procedure employed was the: same asthat Example 1d;= except" that"500 grams of v the ester identified as of Patent 2,542,005? W018ireacted with 82 gramsof octaphenoxyetlioxy ethyl} dimethylaminm The"product, contained xylene and was; a; viscous; dark: axnhep" liquid;giving a somewhat cloudy solution;

5, Example 12d The procedure employed wasthe same as that in Example 1d,exceptthat' 250 grams of the ester identified as 80' of Patent 2,542,005were reacted with 42 grams of cetyldimethylamine. The product contained42.8% xylene and was a viscou s, dark amber liquid, giving av somewhatcloudy solution.

Example 13d The procedure employed was the same as that in Example ld,except that 250 grams of the ester identified as, 9c ofPatent 2,542,005werereacted with 37 grams of octadecenyldimethylamine, The productcontained. 40.6% xylene and was a viscous, dark amber, partly solidmass, giving a clear solution.

Example 1411 I The-procedure employed was the same as that in Example1d, except that 250 grams of the ester identified as 12c of Patent2,542,005 were reacted with 57 grams ofoctaphenoxyethoxyethyldimethylamine. The product contained 47.0% xyleneand was a viscous, darkamber liquid, giving a cloudy solution;

Example 15d The procedure'employed was the same as that in Example 1d,except that 250 grams of the ester identified as 200 of Patent 2,542,005were reacted with 23 grams of dodecyldmethylamine. The product contained38.2% xylene and was a very viscous, dark amber liquid, giving a cloudysolution.

Having thus described our invention, what we claim as new and desire tosecure by Letters Patent is:

l. A quaternary ammonium compound obtained by reaction between adimethylated higher aliphatic amine in which the aliphatic radical hasat least 10 and not more than 22 carbon atoms, and an ester in which theacyl radical is that of an alpha-halogen monocarboxylic acid having notover 6 carbon atoms and composed of carbon, hydrogen, oxygen andhalogen, and the alcoholic radical is that of certain hydrophilepolyhydric synthetic products; said hydrophile synthetic products beingoxyalkylation products of (A) an alpha-beta alkylene oxide having notmore than 4 carbon atoms and selected from the class consisting ofethylene oxide, propylene oxide, butylene oxide, glycide, andmethylglycide, and (B) an oxyalkylation-susceptible, fusible, organicsolvent-soluble, water-insoluble phenol-aldehyde resin; said resin beingderived by reaction between a difunctional monohydric phenol and analdehyde having not over 8 carbon atoms and having one functional groupreactive towards said phenol; said resin being formed in the substantialabsence of phenols of functionality greater than two; said phenol beingof the formula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in one of the positions ortho and para;said oxyalkylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (R1O)n, in

WhiCh RIiiS aimember selected from the class consisting ofethyleneradicals, propylene radicals, butylene radicals,hydroxypropylene radicals, and hydroxybutyl'eneradicals, and n is avnumeral varying from 1. to20; with the proviso that at least -2 moles.of'alkylene oxide be introduced for each phenolic nucleus.

2. A quaternary ammonium compound obtained'by reaction between adimethylated higher aliphatic amine in which the aliphatic radical hasat least 10 and not more than 22 carbon atoms, and a chloroacetate ofcertain hydrophile synthetic products; a said. hydrophilesyntheticproductsbeingoxyalkylation products of (A) an in' which "R" is ahydrocarbon radical having [at least 4 and not more than 12 carbon atomsand substituted in one of the positions ortho and para; saidoxyalkylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (RiOM, in which R1 is a member selected fromthe class consisting of ethylene radicals, propylene radicals, butyleneradicals, hydroxypropylene radicals and hydroxybutylene radicals, and nis a numeral varying from 1 to 20; with the proviso that at least 2moles of alkylene oxide be introduced for each phenolic nucleus; andwith the final proviso that the hydrophile properties of the ultimatequaternary ammonium compound as well as the oxyalkylated resin in anequal weight of xylene are sufificient to produce an emulsion when saidxylene solution is shaken vigorously with one to three volumes of water.

3. A quaternary ammonium compound obtained by reaction between adimethylated higher aliphatic amine in which the aliphatic radical hasat least 10 and not more than 22 carbon atoms, and a chloroacetate ofcertain hydrophile polyhydric synthetic products; said hydrophilesynthetic products being oxyethylation products of (A) ethylene oxide,and (B) an oxyethylationsusceptible, fusible, organic solvent-soluble,water-insoluble phenol-aldehyde resin; said resin being derived byreaction between a difunctional monohydric phenol and an aldehyde havingnot over 8 carbon atoms and having one functional group reactive towardssaid phenol; said resin being formed in the substantial absence ofphenols of functionality greater than two; said phenol being of theformula:

in which R is a hydrocarbon radical having at least 4 and not more than12 carbon atoms and substituted in one of the positions ortho and para;said oxyethylated resin being characterized by the introduction into theresin molecule at the phenolic hydroxyls of a plurality of divalentradicals having the formula (C2H4OM; wherein n is a numeral varying irom1' to 20; with the proviso that at least 2 moles of ethylene oxide beintroduced for each phenolic nucleus; and with the finalproviso that thehydrophile properties cith'e ultimate quaternary ammonium compound aswell as the oxyethylated resin in an equal weight of xylene are'su'flicient to produce an emulsion when said Xylene solution is shakenvigorously with one to three volumes of water.

4. A quaternary ammonium compound obtained by reactionbetw'een adimethvlated higher aliphatic amine in which the aliphatic radical hasat least 10 and not more than 22 carbon atoms, and a chloroacetate ofcertain hydrophile synthetic products; said hydrophile syntheticproducts being oxyethylation products of (A) ethylene oxide, and (B) anoxyethylation-susce'ptible, fusible, organic solvent-soluble,waterinsoluble, low-stage phenol-aldehyde resin having an averagemolecular weight corresponding to at least 3 and not over 7 phenolicnuclei per resin molecule; said resin being derived by reaction betweena difunctional monohydric phenol and formaldehyde; said resin beingformed in the substantial absence of phenols of functionality greaterthan two; said phenol being of the formula:

in which R is an aliphatic ht d rocarbon radical having at least 4andnot. more than 12 carbon atoms and substituted in one of thepositions ortho and para; said oxyethylated resin being characterised bythe introduction into the resin molecule at the phenolic hidroxyls of aplurality of divalent radicals having the formula (Cal-14011;; wherein nis a numeral varying from 1 to 20; with the proviso that at least 2moles of ethylene oxide be introduced for each phenolic nucleus; andwith the final "proviso that the hydl'ephile properties of theultirnatequaternary ammonium compound as well as the oilyethyla-ted resin in anequal weight of ii'y'lehe are sufficient to produce an emulsion whensaid xylene solution is shaken vigorously with one to three volumes ofwater.

5. The product of claim 4, wherein R is substituted in the paraposition.

6. The product of claim 4, wherein R is a blityl radical substituted inthe para position.

'7. The product of claim 4, wherein R is an amyl radical substituted inthe para position.

8. The product of claim 4, wherein R is a nonyl radical substituted inthe para position.

MELVIN DE GROOTE. BERNHARD KEISER.

Name Date De Groote Mar. 7, 1950 Number

1. A QUATERNARY AMMONIUM COMPOUND OBTAINED BY REACTION BETWEEN ADIMETHYLATED HIGHER ALIPHATIC AMINE IN WHICH THE ALIPHATIC RADICAL HASAT LEAST 10 AND NOT MORE THAN 22 CARBON ATOMS, AND AN ESTER IN WHICH THEACYL RADICAL IS THAT OF AN ALPHA-HALOGEN MONOCARBOXYLIC ACID HAVING NOTOVER 6 CARBON ATOMS AND COMPOSED OF CARBON, HYDROGEN, OXYGEN ANDHALOGEN, AND THE ALCOHOLIC RADICAL IS THAT OF CERTAIN HYDROPHILEPOLYHYDRIC SYNTHETIC PRODUCTS; SAID HYDROPHILE SYNTHETIC PRODUCTS BEINGOXYALKYLATION PRODUCTS OF (A) AN ALPHA-BETA ALKYLENE OXIDE HAVING NOTMORE THAN 4 CARBON ATOMS AND SELECTED FROM THE CLASS CONSISTING OFETHYLENE OXIDE, PROPYLENE OXIDE, BUTYLENE OXIDE, GLYCIDE, ANDMETHYLGLYCIDE, AND (B) AN OXYALKYLATION-SUSCEPTIBLE, FUSIBLE, ORGANICSOLVENT-SOLUBLE, WATER-INSOLUBLE PHENOL-ALDEHYDE RESIN; SAID RESIN BEINGDERIVED BY REACTION BETWEEN A DIFUNCTIONAL MONOHYDRIC PHENOL AND ANALDEHYDE HAVING NOT OVER 8 CARBON ATOMS AND HAVING ONE FUNCTIONAL GROUPREACTIVE TOWARDS SAID PHENOL; SAID RESIN BEING FORMED IN THE SUBSTANTIALABSENCE OF PHENOLS OF FUNCTIONALITY GREATER THAN TWO; SAID PHENOL BEINGOF THE FORMULA: